Method of treating hydrocarbons



Jan. 19, 1954 w. E. scovlLL METHOD 0F TREATING HYDROCARBONS 2Sheets-Sheet 1 Filed April 27. 1950 HIS ATTORNEYS.l

W. E. SCOVILL METHOD 0F' TREATING HYDROGARBONS Jan. 19, 1954 2Sheets-Sheet 2 Filed April 27, 1950 3G NS.

nml l HIS ATTORNEYS.

Patented Jan. 19, 1954 l METHOD F TREATING HYDROCARBONS Warner E.Scovill, Lakewood, Ohio, assignor to The Standard Oil Company,Cleveland, Ohio,

a corporation of Ohio Application April 27, 195 0, Serial No. 158,479

3 VClaims. (Cl. 196-52) treating hydrocarbons with a nely dividedadsorbent contact catalytic material in powder form and moreparticularly to a combination of contact adsorption and fluid catalyticcracking processes that may be widely spaced in time and distance,wherein the same material is used as the adsorptionfcontact medium andthefluid cracking catalyst.

To cite an illustrative example without, however, intending to limit thescope of this invention thereto, the principles of this invention may beIapplied to the decolorization of lubricating oils by the contact methodand to the fluid catalytic cracking of hydrocarbons to formv gasoline.By such an application it is possible to utilize aiiuid catalyticcracking unit not only for the cracking of hydrocarbons but, inaddition, for the regeneration of lubricating oil contact material.

The terms "adsorbent contact catalytic material and contact material asused herein refer to finely divided materials having adsorbentproperties as well as catalytic activity. Thesematerials include contactclays and iiuid catalysts generally known in the art to have anextremely small particle size, e. g., about 95% of the particles of anygiven material normally pass through a 20G-mesh screen, and are to bedistinguished from materials such as percolation clays and fixed bedcatalysts, wherein the particles are pellets or granules thatrordinarily do not p-ass through a screen finer than 90 mesh.

It has now been found that the contacting of lubricating oils withadsorbent contact catalytic material for decolorizing the oils has nodeleterious eifect upon the catalytic activity of the material and thatsuch material, after being used as a contact adsorption agent, may beused as catalyst in a fluid cracking operation and, if desired, beregenerated in a uidized regenerating zone for recycling to a contactadsorption or fluid cracking operation, or both. The undesirablehydrocarbons adsorbed on the contact material during the decolorizingstep are subjected tc cracking, and therefore converted into desirablehydrocarbons of lower molecular weight, in the iluid cracking operation.Carbon or coke remaining on the contact material leaving the fluidreactor is burned off in the iluidized 'regenerating zone. 'Ihis is tobe distinguished from methods wherein spent` contact clays orpercolation clays, after contact with a lubricating oil, are mixed witha gas oil charge that is then subjected to thermal cracking in theliquid phase. 'Such methods inherently do not involve removal orconversion of tlieradsorbed hydrocarbons during the cracking step.

The present invention, therefore, contemplates av method of utilizing anadsorbent contact catalytic material or a .combination of several such 2materials, the choice of contact material depending upon requirementsdescribed more fully hereinafter, as both an adsorbent and a fluidcatalyst in a unitary systemor in separate systems. In the preferredembodiment of the invention, a contact material, or combination ofcontact materials is utilized rst as an adsorbent for rening hydrocarbonoils in the liquid phase by the contact method and then as a iiuidcatalyst for the conversion of hydrocarbons suoliv as naphtha-gas oilhydrocarbon fractions. The contact material may then be regenerated andrecycled to theadsorbing unit, the fluid cracking unit, or both.

One of the advantages of this invention is that it provides a simple andeconomical means for regenerating contact materials known primarily fortheir adsorbent properties but nevertheless possessing appreciablecatalytic activity. e Another advantage of the invention, when appliedto a combination of contact decolo'rization and fluid crackingprocesses, is that it provides a simple means for recovering theundesirable hydrocarbons removed from lubricating oils inthe adsorptionprocess and making them available for y* catalytic cracking.

Another advantage of the invention is that .it may be utilized for thetreatment of any lubricating oil whether it be unreiined, solventtreatedor acid treated.

Still another advantage of the invention is that it makes possibleappreciable economies in the operation of a contact'plant, fluidcracking plant, or both.

The contact material employed in the method' of. this invention may beany material having the particle size hereinbefore specified and knownto have adsorptive as well as catalytic properties. rJhe preferredmaterial includes tne silica-aiumina type cataiysts cominoniy rei-erredto as contact clays, suon as members of the group of acid-activated,natui'ai ciays made from tne minerai montmoriilonite, available from theFiltrol Corporation and marketed uriner trade names suon as riltrol and"Super if'iltrol lube contact clays, as weil as nuici catalysts ofthenatural ciay typeavailable under the trade name Fiitrol D and fluidcatalysts maae syntheticaliy by precipitating alumina and silica, whichrai'eavaiiabie Vast/rie spray-dried and oil dropped Microsphere type andDiakeil cataiysts avaiiabie from The Universal Uil rioducts C'oinpanyand M. W. Kellogg Company, respectively.

'lhe method of this invention is further illustrated in the accompanyingdrawing, wherein;

'Figure l is a diagrammatic ow sheet; and Figure 2 is a flow sheetillustrating one preferred embodiment of the method of this inven--tion.

Referring now to Figure 1 of thedrawng, a lubricating oil contact plantI0 and a uid catalytic cracking unit I I may be supplied with contactmaterialin the form of contact clay fromy source I2', "fluid-typecatalyst 'from source .f4 Aor both depending upon "the requirements ofthe contact plant and the fluid cracking unit.

The requirements of a fluid catalytic cracking unit, in so far as theamount of ,makee'up 'catalyst is concerned, depends upon tl'iesizeY ofthe unit, the type of fluidl catalysts, ,and V"otlrne'r l0idiosyncracies of the plant.

The requirements of a lubricating oil contact plant, in so far as theamountbfcontact inea' 'cracking unit -are exactly fb'alanced 4by therequirements Aof a `contact plant, i. e., where the `amount of make-upcatalyst required by the cracking Aunit is equal to the amount "ofcontact material used. in the contact plant inthe same time interval,Vthe whole mass of contact material lleaving the contact plant "may becharged to" the fluid `cracking unit as make-up catalyst. jfn thisembodiment, contact material from `source I2 or I4 or both, in an amountequal 'to 'the make-up catalyst required by the cracking unit I'I, issupplied tothe contact plant I0 by way of lines I6 and I'I or lines I9and II. After the 'spent contact material has been separated from the`cil ycontacted in the contact plant I0, it is passed -by Way of lines20 and '2i to make-'up catalyst storage 22 and from there to the 'fluidcracking unit by Way of lines 24 and 2B. After regeneration, theregenerated contact' material is recycled to the cracking unit by way oflines 21 and v29..

`Where the requirements of a contact plant are limiting, i. e., wherethe amount of contact material used exceeds the amount of make-upcatalyst required by the uid 'catalytic cracking unit, severalalternative procedures in accord-f ance with the present invention arecontemplated.

One such 'procedure is to lo'per'ate'the contact plant cyclically 'with'a high activity fluid catalyst anda Contact cla'y. Thus, forexample,-fresh make-up fluid catalyst and, if desired, regenerated catalyst 'maybe' used 'the contact plant and passedto' the'c'atalytic unit duringonecy cle,'and contact 'clay Vmay be usedin the contact plant and then'disposed of in the other cycle.v Thisprocedure can be varied byintroducing the `fresh make-up catalyst directly into the4 cracking unitand passing an amount of regenerated catalyst equal Kto the amountv offresh, make-up catalyst'to the contact plant for re,- cycling to thecracking unit. Y

Thus, for example', fresh fluid catalystrfrom source I4 in an amountequal to the` make-up catalyst required by the cracking unit l Iislpassed during onecycle into-the contact plant I by way of lines I9and I1 and, after being separated fromthe oil contacted therewith,isfpassed into make-up catalyst storage 22 by Way of lines 20H- and 2|.'Fro'mthis point, the make-up catalyst is. added as required lby Way oflines 24 and' 2.6 to the regenerated catalyst recycled t'o the crackingunit by way'of lines 2I and 29. In the other cycle, fresh contact clayfrom source I2 is supplied to the contact plant I0 by way of lines I6and I1 and, after being separated from the oil contacted therewith, isremoved by Way of lines' ing the first cycle by utilizing fresh uid'catalyst from source I4 directly as the. make-up catalyst. 'This is`vaccomplished by passing it di- `rectlyto the cracking unity II'iby Wayo'f lines 32 4and 26 and passing, to the contact plant I0 by 'Way ofline 34, an amount of regenerated contactA material'fequal-'to theamount of fresh catalyst introduced as make-up catalyst. The regeneratedcatalyst, 'after being separated from the oil contacted `therewith, isrecycled to the cracking unit I'I by way of lines 20 and 2 I, makekupcatalyst 'storage 22 and lines 24 and 26.

This .procedure has the advantage, peculiar to it, 'of operating thefluid catalytic cracking unit at maximum efficiency due to the usetherein of high activity iuid catalysts only, land of reducingsubstantially the amount of contact clay required bythe contactadsorption plant.

EXAMPLE A contactv adsorption plant for decolorizing lubricating oil iny'the' li'quid phase and having 'a capacity for processing 500 barrelsper day of solvent extracted bright stock having a viscosity of SUS at210 F. and requiring 3.75 tons of Filtrol lube contact Yclay Vper day toreduce the optical density of the oil to about 90, was run cyclically onKellogg Diakell uid catalyst and Filtrol lube contact clay. Afluidcatalytic cracking ,plant-l for thev conversion of 15,000 barrelsper'fday of a naphtha-gas oil to gasoline was run on Kellogg Diakell uidcatalyst, the make-up requirements of the cracking being supplied byfluid catalyst from the adsorption plant.

vThe contact plant was-:run for 16 days Aon 60 tons of fresh KelloggDi-akell uid catalyst having an initial Cat A" activity `of 40.7. It was`found that thegoptcal density of 8,000 barrels of oil was reduced toAan average fof 89.0 and that the Cat A lactivity of the catalyst, afterContact with the oil at a rate of 15 pounds per barreLhad increased to41.5. This catalyst was then used for 20 days as make-up catalyst in theiiuid cracking plant.

rIhe contact plantjyvas then run for 4 days on 15 tons of fresh Filtrollube contact clay (2-4.17). It was found that the optical density of2,000 'barrels of oil was reduced to an average of 93.0. j l

An alternative procedure is to operate the contactv plant and the fluidcatalytic cracking unitwith a contact clay alone. Thus, for example, aportion of the spent contact clay from the, contact plant equal to thesum of amounts of make-up and regenerated 'catalyst may be passed to thecracking plant and the regenerated clay maybe recycled to the contactplant, a suincient amount of fresh contact clay being added to thecontact plant to make up for the spent clay notpassed to the crackingunit and for that lost during regeneration. One variation of thisprocedure, if theY capacity of the regenerator permits, Vis to 'passdirectly to ythe regenerator from the contact 'plant the spent clay thatis not passed to the cracking unit..

Thus, for example', fresh contact clay in an amountequal to the' make-uprequirements of the fluid cracking unit I I may be introduced into thecontact plant I0 from source I2 by wayof lines I6 and 'I'I. Aftercontacting the oil in contact plant I0, an amount of the spent clayseparated from the oil lequal to the amount of make-up ycatalystrequiredja'nd the amount of contact material regenerated' Vis passed tothe cracking 'unit"II"b'y 'Way' of lines' 20 and 2l.

namens@ make-up catalyst storage 22 and lines 24 and 26, the balancebeing sent lto clay disposal 3| by way of line 30 and the regeneratedcontact clay being recycled to the contact plant I by Way of lines 21and 34. Y

If the capacity of the regenerator permits, that portion of the spentcontact clay from contact plant l0 not passed to the cracking unit maybe passed directly to the regenerator andA then recycled back to thecontact plant l0 along with the regenerated contact clay from crackingunit This procedure has the advantages, peculiar to it,-oi utilizing tothe fullest the catalytic activity of spent contact clays, ofrecovering, for cracking purposes, an appreciable portion of theLhydrocarbons removed from the lubricating oil in the contact plant, andof utilizing the regenerator of the fluid cracking plant forregenerating contact clay in an economically feasible manner.

Where, on the other hand, the requirements of a fluid catalytic crackingunit are limiting, it is usually preferable to utilize a high activityfluid catalyst in both plants. In this embodiment, a proportion of thecontact material equal to that required by the contact plant iscirculated between the contact plan and the cracking unit and an amountof fresh material equivalent to the amount of make-up catalystrequiredby thev cracking unit is introduced at any desired point in the system.Y Thus, for example, the contact plant vI0 is supplied with the `amountof regenerated catalyst required by Way of line 34, the balance isrecycled directly -to the fluid catalytic cracking unit by Way of line29, and the portion used in the contact plant I0 is recycled to thecracking unit by wayof lines 20 and 2|, make-up catalyst storage 22 andlines 24 and 26. Fresh fluid catalyst from source I4 is used to satisfythe make-up requirements of the cracking unit Il and is-added by way oflines 32 and V26 or, if desired, by Way of lines`|9 and I1, in whichevent the amount of regeneratedcatalyst passed to the contact plant I0by way of' line 34 is reduced so that the total amount of the fluidcatalyst supplied to the contact plant does not exceed its requirements.y y

This method has the advantage, peculiar to it, of making it unnecessaryto provide special contact material for the contact plant while notinterfering with the productivity of the fluid catalytic cracking unit.

Referring now to Figure 2 of the drawing, there is illustrated apreferred embodiment of the invention distinguished by the fact that thecontact material, after having been subjected to contact with oil to beclay treated, which term is intended to, include not only raw oil butoil that has been subjected to solvent refining or acid treatment, ispassed to the reactor unit of the catalytic cracking plant beforeentering the .re-

generator.

In this embodiment a portion of the oil kfrom storage tanks 40 is passedby means of a pump 4| through a heat exchanger 42 directly to a heater44 and another portion is passed'wto the heater 44 Aby Way of a mixingtank 46. Contact material, such as adsorbent clayfrom a hopper 41, isintroduced into the mixing tank 46 Vand from there passed into theheater 44 with the second portion of oil to be treated. The lheatedmixture leaves the heater 44 by'way of line 49, passes through the heatexchanger 42 `andis introduced into a timetank .50 to allow 9.,;Predeftermined ik time of- .contact between; the contact material vand-theoil. From the time tank 50, themixturefis passed into a rotary filter 5|from whence theflltrate passes into a filtratereceiver 52 and ultimatelyto'a receiver for filtered oil.A The contact material leaves therotaryfilter 5|V by. Way of line 54,.-,passes througha'spent clay receiver 56and-is lpumped into the fluid reactor 51 AWith a preheated charge offresh cracking stockfrom charge preheater 59.

Thel charge is subjected to cracking inthe reactor 51 and leaves thereactor at the top by way of lineY 60 to a `fractionator 6| wherein itis re solved into fractions of gas and gasoline, furnace oil,gas oil anda slurry that 4is recycled to the reactor by Way of a thickener 62 andline 64.

The spent clay leaves the uid reactor 51 by way of line 66 and is passedinto the regenerator 61. Thegaseous -eilluents from the regenerator v61are passed through a cyclone separator 69 and leave the system as uegas. A portion of the regenerated clay is recycled ldirectly to thereactor 51 by way of line 10 and another portion of the regenerated clayis recycled to the clay hopper 41 by Way of line 1|. Fresh clay is addedto the clay hopper 41 by Way of line 12.

Tests have revealed that the vcatalytic activity,` as determined by thestandard Cat A test, of commercially available lubricating oil contactclay is 30 or over, and therefore sufcient to be `used as a make-upcatalyst to a fluid catalytic cracking unit. A comparison of thecatalytic activityof one typical lubricating oil contact clay with twohigh activity iluid catalysts is given in Table 1 below:

Table 1 ATALYTIC ATIVITY 0F VARIOUS VLUBE l TACT CLAYS AND FLUIDCATALYSTS 'Cov Tests have also shovvn that the ability of fluid crackingcatalysts to decolorize crude lubricating oil is comparable totheabilityof cheaper contact clays of lesser catalytic activity. Theresults of such tests are listed in Table 2,`the optical density listedin the last Vthree columns being that of 1000 grams of solvent extractedbright stock havingv a viscosityof SUS at 210 F. treated for 30 minutesatei-50F. With the stated amounts of y TabZeZ Optical density Mmm]51m/tbl. 1o 1hs./bb1. 15 1bs./bb1.`

(1.5 weight (3.0 weight (4.5 weight percent) percent) percent) SiliperFi1trollube contact c ay 159. 0

Ilgll lube contact clay 127.3 111.5

Kleuogg Diakelw uuid cata- 144 o 93` 0 ys 147.2 14 F11ttrol" grade Diluid cata- 6 o 89 o U. P. spraddriecMlcroo 3 88 2 sp eres u1 icatyst... 154.0 `114.2 U. O. P. 311 dropped Mcro- 120 5 ,spheresV 178.2203.0 144.0

Further tests showed that the .catalytic activity of neitherthe lessexpensive contact vclays nor the more expensive, high activity fluidcatalysts was `deleteriously affected by contacting them with oils.Table 3 shows ythe effects of contacting, for 30 minutes at 450 F.,'onecontact clay and two high lactivity fluid catalysts with 1000` grainsof heavy steam refined oil having a viscosity of 200 at 210- F. (raw,untreated cylinder stock). Table 4 shows the effect of contacting, for30 minutes at 300' F., a high activity fluid catalyst with a solventextracted bright. stock having a Viscosity of 120 SUS at 2,10'F. Table 5indicates the change in- Cat- A- activ-ity of a contact clay aftercontact with theV same oil under the same conditions.

ACTIV'LTY' QF CRAQKIJNG @ATALYSTS AND 'LIEBE ein ccNrAcr ctms. man i-N.naar: onf. con

'merma Table 3 l Qatwtaercoma Material gt) l n @lbs/.thi

Filtrol contact clay (Xp The change;- in: Cat A activity of" anumber yntact; materials.. as,A well eis-.the optcal dem sity ol-QODigilJll-Smplcs of the cils/after con-.f 1 for- 3,0, minutes at; aMtemperature m16? Hated in; Tables: and@ 7*.. The oil*l extentL k-rlbsaci acidiperibarrel and` the oil'inv testsgreported Table '7;'Wasad'ewafxed iparaflini distillate dey/taxed. by" chilling. andfiltering havaing a viscosity ofi SiO-1,00 SUSziat, 100i E; andi whichhad been acid treated with. ldllbspof-.f aci-d. per barrel.

The catalyst yactivity wasv determined by the standard. Cat A" procedureand the materials used for clay contacting were blown dry with air priorto running the Cat A tests.

The term optical density in the present disfclosure represents thestandard logarithmic ratio of intensity of an incident ray falling on atransparent. or translucent` medium to the intensity of the transmittedray for a sample length of onev meter and light' of wave length from5100 to 5500v Angstrcms.

This application is a continuation-in-part of my earlier co-pendingapplication Serial No. 385779, filed- July 15, 1948, now abandoned.

It is to be understood that innumerable variations and modificationsWill' immediately become apparenty to.- those skilled in the art uponreading the foregoing disclosure; The invention contempla-tes all suchvariations and modiiications as come Within the scope of the appendedclaims.

I claim:

l. A method of treating hydrocarbons which comprises contacting alubricating oil in the liquid phase in a ccntactzone with a iinelydivi`ded, adsorbent silica-alumina contact catalytic material, havingboth adsorbent and catalytic properties and a, particule size such thatabout 95% of t-he particles pass through a 20G-mesh screen, fordecolorizing ,said lubricating oil', separating said ,material from thedecolori'zed oil, cracking hydrocarbons in a fluid catalytic crackingzoney by Contact with said separated contact catalytic material,regenerating said contact material in a iluiclized' regenerating zone,and recycling said regenerated ccntact material successively to saidcontact and fluid catalytic cracking zones.

2;. A methodn off treating hydrocarbons which comprises contacting alubricating oil in the liquid phaseY in a contact Zone with a nelydiyided, adsorbent silica-aluniina contact clay, having both adsorbentand' catalytic properties and a particle size such, that about 95% ofthe particles pass through a ZOO-meshscreen, for decolorizing saidlubricating oil, separating said Contact clay from the decolorized oil,cracking hydrocarbons in a ri 'fluid catalytic cracking zone by contactwith said separated contact clay, regeneratingA said contact cl'ayinV a;fluidized' regenerating zone, and recycling, said regenerated contactclay successively tosaid:Contactl and'fiuid catalytic cracking zones.

3*; A methodA oi'i treating hydrocarbons which comprisescontactingalubricating oil in the liquid phase in a' contactv zone with asilica-alumina 'uid catalyst, having both adsorbentv andcatalytic-'properties and-` aY particle size such that about 95% of theparticles passthrough a 200- mesh screen; for dccolorizing, saidlubricating oil, separating'said'iiuid catalyst from the decolorizedoiliwcracking hydrocarbon-s ina Il uidV catalytic cracking"zoneY bycontact" with' said .separated fluidi 753 catalyst; -regenerating lsaidyiiuid catalyst in a fluidzed regenerating zone, and recycling saidNumber Name Date regenerated fluid catalyst successively to said con-2,416,'729 Arveson Mar. 4, 1947 tact and uid catalytic cracking zones;2,549,518 Perry Apr. 17, 1951v WARNER E. SCOVILL.

5 OTHER REFERENCES References Cted m the fue of "uns patent Double-DutyCatalyst, by George West, Oil and UNITED STATES PATENTS Gas Journal,vOctober 19, 1950, Vol. 49, No. 42, Number Nme Date pages 78, r19, 118,and 120.

2,091,892 Stratfrd Aug. 31, 1937 10

1. A METHOD OF TREATING HYDROCARBONS WHICH COMPRISES CONTACTING ALUBRICATING OIL IN THE LIQUID PHASE IN A CONTACT ZONE WITH A FINELYDIVIDED, ADSORBENT SILICA-ALUMINA CONTACT CATALYTIC MATERIAL, HAVINGBOTH ADSORBENT AND CATALYTIC PROPERTIES AND A PARTICULE SIZE SUCH THATABOUT 95% OF THE PARTICLES PASS THROUGH A 200-MESH SCREEN, FORDECOLORIZING SAID LUBRICATING OIL, SEPARATING SAID MATERIAL FROM THEDECOLORIZED OIL, CRACKING HYDROCARBONS IN A FLUID CATALYTIC CRACKINGZONE BY CONTACT WITH SAID SEPARATED CONTACT CATALYTIC MATERIAL,REGENERATING SAID CONTACT MATERIAL IN A FLUIDIZED REGENERATING ZONE, ANDRECYCLING SAID REGENERATED CONTACT MATERIAL SUCCESSIVELY TO SAID CONTACTAND FLUID CATALYTIC CRACKING ZONES.